Water thermochemical

Thermochemical Liquefaction. Most of the research done since 1970 on the direct thermochemical Hquefaction of biomass has been concentrated on the use of various pyrolytic techniques for the production of Hquid fuels and fuel components (96,112,125,166,167). Some of the techniques investigated are entrained-flow pyrolysis, vacuum pyrolysis, rapid and flash pyrolysis, ultrafast pyrolysis in vortex reactors, fluid-bed pyrolysis, low temperature pyrolysis at long reaction times, and updraft fixed-bed pyrolysis. Other research has been done to develop low cost, upgrading methods to convert the complex mixtures formed on pyrolysis of biomass to high quaHty transportation fuels, and to study Hquefaction at high pressures via solvolysis, steam—water treatment, catalytic hydrotreatment, and noncatalytic and catalytic treatment in aqueous systems. 

Multistep Thermochemical Water Splitting. Multistep thermochemical hydrogen production methods are designed to avoid the problems of one-step water spHtting, ie, the high temperatures needed to achieve appreciable AG reduction, and the low efficiencies of water electrolysis. Although water electrolysis itself is quite efficient, the production of electricity is inefficient (30—40%). This results in an overall efficiency of 24—35% for water electrolysis. 

In multistep thermochemical water spHtting, two or more reactions are used to produce hydrogen from water. A hypothetical example is... 

Two of these cycles have an electrolysis step. Although one of the purposes of the thermochemical cycles is to avoid electrolysis and the associated iaefftciencies of electricity production, the electrolysis steps proposed use much less electrical energy than water electrolysis. The Mark 13 is regarded as the most advanced thermochemical cycle, with overall efficiency of about 40%, including the electrolysis step (164). 

A detailed discussion of thermochemical water splitting is available (155,165—167). Whereas many problems remain to be solved before commercia1i2ation is considered, this method has the potential of beiag a more efficient, and hence more cost-effective way to produce hydrogen than is water electrolysis. 

The physical properties of bismuth, summarized ia Table 1, are characterized by a low melting poiat, a high density, and expansion on solidification. Thermochemical and thermodynamic data are summarized ia Table 2. The soHd metal floats on the Hquid metal as ice floating on water. GaUium and antimony are the only other metals that expand on solidification. Bismuth is the most diamagnetic of the metals, and it is a poor electrical conductor. The thermal conductivity of bismuth is lower than that of any other metal except mercury. 

Non-electrolytic sources of hydrogen have also been studied. The chemical problem is how to transfer the correct amount of free energy to a water molecule in order to decompose it. In the last few years about I0(X)0 such thermochemical water-splitting cycles have been identified, most of them with the help of computers, though it is significant that the most promising ones were discovered first by the intuition of chemists. 

Electrolysis, and thermochemical and photochemical decomposition of water followed by purification through diffusion methods are expensive processes to produce hydrogen. 

To see where a thermochemical equation comes from, consider the process by which ammonium nitrate dissolves in water ... 

Self-Tfst 6.11B When 0.338 g of pentane, C5H12, burns in an excess of oxygen to form carbon dioxide and liquid water in the same calorimeter as that used in Self-Test 6.1 1A, the temperature rises by 76.7°C. Write the thermochemical equation for the reaction. 

In formulating a set of bond-energy values we first calculated the energies of formation of molecules from experimental values of the heats of combustion of the compounds6 and thermochemical data pertaining to the products of combustion—carbon dioxide, water, nitrogen, etc. The same values for the latter quantities were used as previously.4... 

Because of uncertainties of equilibrium constants, ES, pH, temperature, /02 and other parameters (activity coefficient, ionic strength, activity of water, pressure), the estimated values of concentrations may have uncertainties of 1 in logarithmic unit. However, it can be concluded from the thermochemical calculations and fluid inclusion data that the Kuroko ore fluids have the following chemical features. 

The variations in Fe and Mg contents of the 14 A Fe-chlorite-14 A Mg-chlorite solid solution are considered here. However, structural formulae for chlorite are not as simple as those considered here. As mentioned by Walshe and Solomon (1981), Stoesell (1984), Cathelineau and Nieva (1985) and Walshe (1986), chlorite solid solution may be represented by six components, and accurate thermochemical data on each end-member component at the hydrothermal conditions of concern are necessary to provide a far more rigorous calculation of the equilibrium between chlorite and hydrothermal solution. However, the above argument demonstrates that the composition of chlorite is a highly useful indicator of physicochemical conditions of hydrothermal solution and extent of water-rock interaction. 

Gangue minerals and salinity give constraints on the pH range. The thermochemical stability field of adularia, sericite and kaolinite depends on temperature, ionic strength, pH and potassium ion concentration of the aqueous phase. The potassium ion concentration is estimated from the empirical relation of Na+/K+ obtained from analyses of geothermal waters (White, 1965 Ellis, 1969 Fournier and Truesdell, 1973), experimental data on rock-water interactions (e.g., Mottl and Holland, 1978) and assuming that salinity of inclusion fluids is equal to ffZNa+ -h m + in which m is molal concentration. From these data potassium ion concentration was assumed to be 0.1 and 0.2 mol/kg H2O for 200°C and 250°C. 

Previous studies clearly indicated that the chemical compositions of geothermal waters are intimately related both to the hydrothermal alteration mineral assemblages of country rocks and to temperature. Shikazono (1976, 1978a) used a logarithmie cation-Cl concentration diagram to interpret the concentrations of alkali and alkaline earth elements and pH of geothermal waters based on thermochemical equilibrium between hydrothermal solution and alteration minerals. 

Figure 253. Thermochemical storage system (Humidifier, water tank and control unit in the front from left to right, three Zeolite modules in the back)...

Thermochemical Water Splitting by Iodine-Sulfur Cycle.137... 

---